Graphene shell-encapsulated copper-based nanoparticles (G@Cu-NPs) effectively activate peracetic acid for elimination of sulfamethazine in water under neutral condition.

In this study, a graphene shell-encapsulated copper-based nanoparticles (G@Cu-NPs) was prepared and employed for peracetic acid (PAA) activation. The characterization of G@Cu-NPs confirmed that the as-prepared material was composed of Cu0 and Cu2O inside and encapsulated by a graphene shell. Experimental results suggested that the synthesized G@Cu-NPs could activate PAA to generate free radicals for efficiently removing sulfamethazine (SMT) under neutral condition. The formation of graphene shells could strongly facilitated electron transfer from the core to the surface. Radical quenching experiments and electron spin resonance (ESR) analysis confirmed that organic radicals (R-O•) and hydroxyl radicals (•OH) were generated in the G@Cu-NPs/PAA system, and R-O• (including CH3CO3• and CH3CO2•) was the main contributor to the elimination of SMT. The possible SMT degradation pathways and mechanisms were proposed, and the toxicity of SMT and its intermediates was predicted with the quantitative structure-activity relationship (QSAR) analysis. Besides, the effects of some key parameters, common anions, and humic acid (HA) on the removal of SMT in the G@Cu-NPs/PAA system were also investigated. Finally, the applicability of G@Cu-NPs/PAA system was explored, showing that the G@Cu-NPs/PAA system possessed satisfactory adaptability to treat different water bodies with admirable reusability and stability.

Advanced oxidation processes for water purification using percarbonate: Insights into oxidation mechanisms, challenges, and enhancing strategies.

Percarbonate (SPC) has drawn considerable attention due to its merits in the safety of handling and transport, stability, and price as well as environmental friendliness, which has been extensively applied in advanced oxidation processes (AOPs) for water decontamination. Nevertheless, comprehensive information on the application of SPC-AOPs for the treatment of organic compounds in aquatic media is scarce. Hence, the focus of this review is to shed light on the mechanisms of reactive oxygen species (ROS) evolution in typical SPC-AOPs (i.e., Fenton-like oxidation, photo-assisted oxidation, and discharge plasma-involved oxidation processes). These SPC-AOPs enable the formation of multiple reactive species like hydroxyl radical (•OH), superoxide radical (O2•-), singlet oxygen (1O2), carbonate radicals (CO3•-), and peroxymonocarbonate (HCO4-), which together or solely contribute to the degradation of target pollutants. Simultaneously, the potential challenges in practical applications of SPC-AOPs are systematically discussed, which include the influence of water quality parameters, cost-effectiveness, available active sites, feasible activation approaches, and ecotoxicity. Subsequently, enhancing strategies to improve the feasibility of SPC-AOPs in the practical implementation are tentatively proposed, which can be achieved by introducing reducing and chelating agents, developing novel activation approaches, designing multiple integrated oxidation processes, as well as alleviating the toxicity after SPC-AOPs treatment. Accordingly, future perspectives and research gaps in SPC-AOPs are elucidated. This review will hopefully offer valuable viewpoints and promote the future development of SPC-AOPs for actual water purification.

Insights into the correlation between different adsorption/oxidation/catalytic performance and physiochemical characteristics of Fe-Mn oxide-based composites.

Fe-Mn oxide-based composites have been widely used in the solidification of heavy metals or the removal of organic pollutants, which can not only show excellent adsorption/oxidation performance, but also show catalytic activity for common oxidants. At present, the correlation between adsorption/oxidation/catalytic performance and physicochemical characteristics of these composites, and the underlying mechanisms are still unclear. Therefore, the main purpose of this review is to disclose the internal relationship between the physicochemical properties of Fe-Mn oxide-based composites and the pollutant removal performance. From the perspective of crystal phase, the basic units of Fe-Mn oxide composites are divided into Fe-Mn binary oxide (FMBO) and spinel MnFe2O4, and the two species were discussed separately in most chapters. The selected physicochemical properties mainly include the type of Fe-Mn oxide composites, surface-to-volume ratio, pore volume, pHpzc, crystal type, surface functional groups. Because the physicochemical properties that determine how effective Fe-Mn oxide material is at removing contaminants may differ as it performs different functions, we discussed the above problems under different application scenarios (adsorption, oxidation, and advanced oxidation process). Additionally, internal factor (Fe/Mn mole ratio) and external factors (pHini, co-ions and ionic strength) were analyzed, and several common synthetic strategies of these composites were presented.

Sulfur or nitrogen-doped rGO supported Fe-Mn bimetal - organic frameworks composite as an efficient heterogeneous catalyst for degradation of sulfamethazine via peroxydisulfate activation.

In this work, sulfur/nitrogen modified reduced graphene oxide (S/N-rGO) was employed as both electron shuttle and support to fabricate Fe-Mn bimetallic organic framework@S/N-rGO hybrids (BOF@S/N-rGO) via a facile two-step solvothermal route. Compared with the transition metal ions (Fe2+/Mn2+), the classical metal oxide catalyst (Fe2O3 and Fe3O4) and nano zero-valent iron (nZVI), BOF@S/N-rGO catalyst can more effectively activate peroxydisulfate (PDS) with ultra-low concentration (0.05 mM) to degrade sulfamethazine (SMT). Quenching experiments, electron paramagnetic resonance (EPR) measurement and linear sweep voltammetry (LSV) showed that the activation pathways of PDS between the two catalysts were different. In BOF@N-rGO+PDS system, the degradation of SMT was mainly attributed to the oxidation of radicals including SO4•- and •OH, especially SO4•- . However, in BOF@S-rGO+PDS system, in addition to the radical pathway, there are also non-radical pathways, namely 1O2 and direct electron transfer. Furthermore, the applicability of BOF@S/N-rGO used in the PDS-mediated advanced oxidation processes (AOPs) was systematically investigated in terms of the effects of operating parameters and coexisting substance (anions and humic acid (HA)), the degradation of other pollutants, as well as the stability and reusability of the catalyst. This study proved that BOF@S/N-rGO was a promising activator of PDS with ultra-low concentration for the degradation of SMT.

Insights into a novel CuS/percarbonate/tetraacetylethylenediamine process for sulfamethazine degradation in alkaline medium.

This work presents a novel CuS/percarbonate/tetraacetylethylenediamine (CuS/SPC/TAED) process for the degradation of sulfamethazine (SMT). Results indicated that the CuS/SPC/TAED process enabled the efficient generation of peracetic acid (PAA), which can be efficiently activated by CuS in alkaline reaction media, and 93.6% of SMT was degraded in 30 min. Mechanism study revealed that the available reactive oxygen species (ROS) including hydroxyl radical (•OH), carbonate radical (CO3•-), superoxide radical (O2•-), singlet oxygen (1O2), and organic radicals (R-O•). Among them, R-O• (acetyloxyl radical (CH3CO2•) and acetylperoxyl radical (CH3CO3•)) were confirmed to be the primary species that contributed to SMT degradation. Simultaneously, the role of sulfur species and carbonate ions were explored. It was found that the reductive O2•- and sulfur species rendered the efficient redox of Cu species. Besides, the effects of key influencing factors including SPC/TAED mole ratio, CuS dosage, initial pH, temperature, and nontarget matrix constituents on SMT degradation were examined. Finally, the degradation intermediates of SMT was identified, and the toxicity of these products was estimated by quantitative structure-activity relationship (QSAR) analysis. Overall, this work offers a new and simple strategy for antibiotic-polluted water remediation.

Degradation of sulfamethazine in water by sulfite activated with zero-valent Fe-Cu bimetallic nanoparticles.

In this work, zero-valent Fe-Cu bimetallic nanoparticles were synthesized using a facile method, and applied to activate sulfite for the degradation of sulfamethazine (SMT) from the aqueous solution. The key factors influencing SMT degradation were investigated, namely the theoretical loading of Cu, Fe-Cu catalyst dosage, sulfite concentration and initial solution pH. The experimental results showed that the Fe-Cu/sulfite system exhibited a much better performance in SMT degradation than the bare Fe0/sulfite system. The mechanism and possible degradation pathway of SMT in Fe-Cu/sulfite system were revealed. The reactive radicals that played a dominant role in the SMT degradation process were •OH and SO4•-, while the loading of Cu induced the synergistic effect between Fe and Cu. The redox cycle between Cu(I)/Cu(II) remarkably contributed to the conversion of Fe(III) to Fe(II), greatly enhancing the catalytic performance of Fe-Cu bimetal. In real groundwater applications, the Fe-Cu/sulfite system also exhibited satisfactory SMT degradation. The 30-day aging tests of Fe-Cu particles demonstrated that the aging of catalyst was not obviously affecting the removal of SMT. Furthermore, the reusability of catalyst was evidenced by the recycling experiments. This study provides a promising application of bimetal activated sulfite for enhanced contaminant degradation in groundwater.